Herbicidal cyclohexane-1,3-dione derivatives

ABSTRACT

The invention concerns novel compounds of the formula I ##STR1## wherein: A, B and D are selected from CH and N; 
     E is selected from oxygen and sulfur; 
     X are selected from halogen, nitro, cyano, alkyl, substituted alkyl, hydroxy, alkoxy, substituted alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, acyloxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, sulfamoyl, substituted sulfamoyl, alkanoyloxy, benzyloxy, substituted benzyloxy, phenyl, substituted phenyl, amino, substituted amino, and the groups formyl and alkanoyl and the oxime, imine and Schiff base derivatives thereof; 
     R 1  is selected from hydrogen, alkyl, alkenyl, alkynyl, substituted alkyl, alkylsulfonyl, arylsulfonyl, acyl and an inorganic or organic cation; 
     R 2  is selected from alkyl substituted alkyl, alkenyl, haloalkenyl, alkynyl and haloalkynyl; 
     R 3  is selected from alkyl, fluoroalkyl, alkenyl, alkynyl, and phenyl; 
     R 4  is selected from hydrogen, halogen, alkyl, cyano and alkoxycarbonyl; and 
     n is 0 or an integer chosen from 1 and 2. 
     The compounds of the invention show herbicidal properties and plant growth regulating properties and in further embodiments the invention provides processes for the preparation of compounds of formula I, intermediates useful in the preparation of the compounds of formula I, compositions containing as active ingredient a compound of formula I, and herbicidal and plant growth regulating processes utilizing compounds of formula I.

This is a division of application Ser. No. 604,967 filed Apr. 27, 1984,now U.S. Pat. No. 4,604,132.

This invention relates to organic compounds having biological activityand in particular to organic compounds having herbicidal properties andplant growth regulating properties, to processes for the preparation ofsuch compounds, to intermediates useful in the preparation of suchcompunds and to herbicidal compositions and processes utilizing suchcompounds and to plant growth regulating compositions and processesutilizing such compounds.

The use of certain cyclohexane-1,3-dione derivatives as grass herbicidesis known in the art. For Example, the "Pesticide Manual" (C R WorthingEditor, The British Crop Protection Council, 6th Edition 1979) describesthe cyclohexane-1,3-dione derivative known commercially asalloxydim-sodium (methyl3-[1-(allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylate) and its use as a grass herbicide. This compound isdisclosed in Australian Pat. No. 464 655 and its equivalents such as UKPat. No. 1 461 170 and U.S. Pat. No. 3,950,420.

More recently, at the 1980 British Crop Protection Conference ("1980British Crop Protection Conference--Weeds, Proceedings Vol 1, ResearchReports", pp 39 to 46, British Crop Protection Council, 1980), a newcyclohexane-1,3-dione grass herbicide code named NP 55()2-N-ethoxybutrimidoyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one)was announced. This compound is disclosed in Australian Pat. No. 503 917and its equivalents.

It has now been found that a new group of cyclohexane-1,3-dionederivatives which have a 5-(5-membered heteroaryl ring) substituentexhibit particularly useful herbicidal activity.

Accordingly the invention provides a compound of formula ##STR2##wherein

A, B and D are independently selected from CH and N provided that atleast one of A, B and D is selected from N;

E is selected from oxygen and sulfur;

X, which may be the same or different, are independently selected fromthe group consisting of: halogen; nitro; cyano; C₁ to C₆ alkyl; C₁ to C₆alkyl substituted with a substituent selected from the group consistingof halogen, nitro, hydroxy, C₁ to C₆ alkoxy and C₁ to C₆ alkylthio; C₂to C₆ alkenyl; C₂ to C₆ alkynyl; hydroxy; C₁ to C₆ alkoxy; C₁ to C₆alkoxy substituted with a substituent selected from halogen and C₁ to C₆alkoxy; C₂ to C₆ alkenyloxy; C₂ to C₆ alkynyloxy; C₂ to C₆ alkanoyloxy;(C₁ to C₆ alkoxy)carbonyl; C₁ to C₆ alkylthio; C₁ to C₆ alkylsulfinyl;C₁ to C₆ alkylsulfonyl; sulfamoyl; N-(C₁ to C₆ alkyl)sulfamoyl;N,N-di(C₁ to C₆ alkyl)-sulfamoyl; benzyloxy; substituted benzyloxywherein the benzene ring is substituted with from one to threesubstituents selected from the group consisting of halogen, nitro, C₁ toC₆ alkyl, C₁ to C₆ alkoxy and C₁ to C₆ haloalkyl; phenyl; substitutedphenyl wherein the benzene ring is substituted with from one to threesubstituents selected from the group consisting of halogen, nitro, C₁ toC₆ alkyl, C₁ to C₆ alkoxy and C₁ to C₆ haloalkyl; the group NR⁵ R⁶wherein R⁵ and R⁶ are independently selected from the group consistingof hydrogen, C₁ to C₆ alkyl, C₂ to C₆ alkanoyl, benzoyl and benzyl; thegroups formyl and C₂ to C₆ alkanoyl and the oxime, imine and Schiff basederivatives thereof;

R¹ is selected from the group consisting of: hydrogen; C₁ to C₆ alkyl;C₂ to C₆ alkenyl; C₂ to C₆ alkynyl; substituted C₁ to C₆ alkyl whereinthe alkyl group is substituted with a substituent selected from thegroup consisting of C₁ to C₆ alkoxy, C₁ to C₆ alkylthio, phenyl andsubstituted phenyl wherein the benzene ring is substituted with from oneto three substituents selected from the group consisting of halogen,nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁to C₆ alkylthio; C₁ to C₆ alkyl sulfonyl; benzenesulfonyl; substitutedbenzenesulfonyl wherein the benzene ring is substituted with from one tothree substituents selected from the group consisting of halogen, nitro,cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁ to C₆alkylthio; an acyl group; and an inorganic or organic cation;

R² is selected from the group consisting of: C₁ to C₆ alkyl; C₂ to C₆alkenyl; C₂ to C₆ haloalkenyl; C₂ to C₆ alkynyl; C₂ to C₆ haloalkynyl;substituted C₁ to C₆ alkyl wherein the alkyl group is substituted with asubstituent selected from the group consisting of halogen, C₁ to C₆alkoxy, C₁ to C₆ alkylthio, phenyl and substituted phenyl wherein thebenzene ring is substituted with from one to three substituents selectedfrom the group consisting of halogen, nitro, cyano, C₁ to C₆ alkyl, C₁to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁ to C₆ alkylthio;

R₃ is selected from the group consisting of: C₁ to C₆ alkyl; C₁ to C₆fluoroalkyl; C₂ to C₆ alkenyl; C₂ to C₆ alkynyl; and phenyl;

R₄ is selected from the group consisting of: hydrogen; halogen; cyano;C₁ to C₆ alkyl; and (C₁ to C₆ alkoxy)carbonyl; and

n is 0 or an integer chosen from 1 and 2.

When in the compound of formula I X is chosen from the groups formyl andC₂ to C₆ alkanoyl and the oxime, imine and Schiff base derivativesthereof, the nature of the oxime, imine and Schiff base derivatives isnot narrowly critical. Although not intending to be bound by theory, itis believed that in the plant the (substituted) imine group may beremoved to give the corresponding compound of formula I in which X isformyl or C₂ to C₆ alkanoyl. Suitable values for the groups formyl andC₂ to C₆ alkanoyl and the oxime, imine and Schiff base derivativesthereof include groups of the formula --C(R⁷)═NR⁸ wherein R⁷ is chosenfrom hydrogen and C₁ to C₅ alkyl, and R⁸ is chosen from hydrogen, C₁ toC₆ alkyl, phenyl, benzyl, hydroxy, C₁ to C₆ alkoxy, phenoxy andbenzyloxy.

When in the compound of formula I R¹ is chosen from acyl the nature ofthe acyl group is not narrowly critical. Although not intending to bebound by theory, it is believed that when R¹ is acyl the acyl group maybe removed in the plant by hydrolysis to give the corresponding compoundof formula I in which R¹ is hydrogen. Suitable acyl groups include:alkanoyl, for example C₂ to C₆ alkanoyl; aroyl, for example benzoyl andsubstituted benzoyl wherein the benzene ring is substituted with fromone to three substituents chosen from the group consisting of halogen,nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁to C₆ alkylthio; and heteroaroyl, for example 2-furoyl, 3-furoyl,2-thenoyl and 3-thenoyl.

When in the compound of formula I R¹ is chosen from an inorganic ororganic cation the nature of the cation is not narrowly critical.Although not intending to be bound by theory, it is believed that whenR¹ is a cation the cation may be removed in the plant to give a compoundof formula I wherein R¹ is hydrogen. Suitable inorganic cations includethe alkali and alkaline earth metal ions, heavy metal ions including thetransition metal ions, and the ammonium ion. Suitable organic cationsinclude the cation R⁹ R¹⁰ R¹¹ R¹² N⁺ wherein R⁹, R¹⁰, R¹¹ and R¹² areindependently chosen from the group consisting of: hydrogen; C₁ to C₁₀alkyl; substituted C₁ to C₁₀ alkyl wherein the alkyl groups issubstituted with a substituent chosen from the group consisting ofhydroxy, halogen and C₁ to C₆ alkoxy; phenyl; benzyl; and the groupssubstituted phenyl and substituted benzyl wherein the benzene ring issubstituted with from one to three substituents chosen from the groupconsisting of halogen, nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl,C₁ to C₆ alkoxy and C₁ to C₆ alkylthio.

It should be recognized that when R₁ is hydrogen the compounds of theinvention may exist in any one of four tautomeric forms as shown belowwherein φ represents the group ##STR3##

The compounds of the invention include: oxazole and thiazole derivativesof formulae Ia to If ##STR4## isoxazole and isothiazole derivatives offormula Ig to Il ##STR5## 1,2,3-oxadiazoles and 1,2,3-thiadiazoles offormula Im to Ip ##STR6## 1,2,4-oxadiazoles and 1,2,4-thiadiazoles offormula Iq to It; ##STR7## 1,3,4-oxadiazoles and 1,3,4-thiadiazoles offormula Iu and Iv ##STR8## 1,2,3,4-oxadiazoles and 1,2,3,6-thiadiazolesof formulae Iw and Ix ##STR9##

Preferred compounds of the invention include those compounds of formulaI wherein:

A, B and D are independently selected from CH and N;

E is selected from oxygen and sulfur;

X, which may be the same or different, are independently selected fromthe group consisting of C₁ to C₆ alkyl, C₁ to C₆ alkoxy, C₁ to C₆alkylthio, halogen, amino, N-(C₁ to C₆ alkyl)amino, N,N-di(C₁ to C₆alkyl)amino, C₂ to C₆ alkanoyl, phenyl, substituted phenyl wherein thebenzene ring is substituted with from one to three substituents selectedfrom the group consisting of halogen, nitro, C₁ to C₆ alkyl, C₁ to C₆alkoxy and C₁ to C₆ haloalkyl, and C₁ to C₆ alkyl substituted with asubstituent selected from the group consisting of halogen, nitro,hydroxy, C₁ to C₆ alkoxy and C₁ to C₆ alkylthio;

R¹ is selected from the group consisting of: hydrogen; C₂ to C₆alkanoyl; benzoyl and substituted benzoyl wherein the benzene ring issubstituted with from one to three substituents selected from the groupconsisting of halogen, nitro, C₁ to C₆ alkyl and C₁ to C₆ alkoxy;benzenesulfonyl and substituted benzenesulfonyl wherein the benzene ringis substituted with from one to three substituents selected from thegroup consisting of halogen, nitro, C₁ to C₆ alkyl and C₁ C₆ alkoxy; andan inorganic or an organic cation selected from the alkali metals suchas lithium, potassium and sodium, the alkaline earth metals such asmagnesium, calcium and barium, the transition metals such as manganese,copper, zinc, iron, nickel, cobalt and silver, the ammonium ion and thetri- and tetra-(alkyl)ammonium ions wherein alkyl is selected from C₁ toC₆ alkyl and C₁ to C₆ hydroxyalkyl;

R² is selected from the group consisting of C₁ to C₆ alkyl, C₂ to C₆alkenyl, C₂ to C₆ alkynyl, C₁ to C₆ haloalkyl, C₂ to C₆ haloalkenyl andC₂ to C₆ haloalkynyl;

R³ is selected from C₁ to C₆ alkyl;

R⁴ is selected from hydrogen, halogen and (C₁ to C₆ alkoxy)carbonyl; and

n is zero or an integer selected from 1 and 2.

More preferred compounds of the invention include those compounds offormula I wherein:

A, B and D are selected from CH and N provided that no more than two ofA, B and D is selected from N;

E is selected from oxygen and sulfur;

X which may be the same or different, are independently selected fromthe group consisting of C₁ to C₆ alkyl, C₁ to C₆ alkoxy, C₁ to C₆alkylthio, halogen, amino, N-(C₁ to C₆ alkyl)amino, N,N-di(C₁ to C₆alkyl)amino, phenyl and C₁ to C₆ alkyl substituted with C₁ to C₆ alkoxy;

R¹ is selected from the group consisting of hydrogen, benzoyl and thealkali metals;

R² is selected from the group consisting of C₁ to C₆ alkyl, C₁ to C₆haloalkyl, C₂ to C₆ alkenyl and C₂ to C₆ alkynyl;

R³ is selected from the group consisting of C₁ to C₆ alkyl;

R⁴ is hydrogen; and

n is zero or an integer selected from 1 and 2.

Even more preferred compounds of the invention include those compoundsof formulae: ##STR10## wherein:

E is selected from oxygen and sulfur;

X, which may be the same or different, are independently selected fromthe group consisting of halogen, C₁ to C₃ alkyl, C₁ to C₃ alkoxy and C₁to C₃ alkylthio;

R¹ is selected from the group consisting of hydrogen and the alkalimetals;

R² is selected from the group consisting of C₁ to C₃ alkyl, C₁ to C₃fluoroalkyl, allyl and propargyl;

R³ is selected from the group consiting of C₁ to C₃ alkyl;

R⁴ is hydrogen; and

n is zero or an integer selected from 1 and 2.

Particularly preferred values for X include methyl, methoxy, methylthioand chlorine;

Particularly preferred values for R¹ include hydrogen and the alkalimetals.

Particularly preferred values for R² include ethyl, fluoroethyl, allyland propargyl.

Particularly preferred values for R³ include ethyl and n-propyl.

Particularly preferred R⁴ is hydrogen.

Particularly preferred n is zero or an integer selected from 1 and 2.

Specific examples of the compounds of the invention include thosecompounds detailed in Tables 1a, 1b and 1c below.

                  TABLE 1a                                                        ______________________________________                                         ##STR11##                                                                    Com-                                                                          pound                                                                         No   (X).sub.n    Link   R.sup.1                                                                           R.sup.2   R.sup.3                                                                             R.sup.4                          ______________________________________                                         1   all H        2      H   C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                 2   4,5-(CH.sub.3).sub.2                                                                       2      H   C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                 3   2-CH.sub.3   5      H   C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                 4   2-C.sub.6 H.sub.5                                                                          5      H   C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                 5   2,4-(CH.sub.3).sub.2                                                                       5      H   C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                 6   2-CH.sub.3   4      H   C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                 7   2-CH.sub.3 S 5      H   C.sub.2 H.sub. 5                                                                        C.sub.2 H.sub.5                                                                     H                                 8   2-(CH.sub.3).sub.2 N4-CH.sub.3                                                             5      H   C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                 9   4-CH.sub.3   2      H   C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                10   5-Br4-CH.sub.3                                                                             2      H   C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                     H                                11   a            2      H   C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                12   2-Cl         5      H   C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                     H                                13   2-CH.sub.3 O 5      H   C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                     H                                14   5-CH.sub.3   2      H   C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                     H                                15   4,5-(CH.sub.3).sub.2                                                                       2      H   C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                     H                                16   2-Cl         5      H   C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                     b                                17   2-CH.sub.3   4      H   CH.sub.2 CHCH.sub.2                                                                     n-C.sub.3 H.sub.7                                                                   H                                18   2-CH.sub.3   4      H   CH.sub.2 CH.sub.2 F                                                                     n-C.sub.3 H.sub.7                                                                   H                                19   2-CH.sub.3   4      H   CH.sub.2 CCH                                                                            n-C.sub.3 H.sub.7                                                                   H                                20   4,5-(CH.sub.3).sub.2                                                                       2      c   C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                21   2-CH.sub.3   4      Na  C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                                                                   H                                ______________________________________                                         Code:                                                                         a  5(CH.sub.3 OCH.sub.2 CH.sub.2)4-CH.sub.3                                   b  CO.sub.2 CH.sub.3                                                          c  COC.sub.6 H.sub.5                                                     

                  TABLE 1b                                                        ______________________________________                                         ##STR12##                                                                    Com-                                                                          pound                                                                         No    (X).sub.n E       Link R.sup.1                                                                            R.sup.2   R.sup.3                           ______________________________________                                        22    3,5-(CH.sub.3).sub.2                                                                    O       4    H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                   23    3-CH.sub.3                                                                              S       5    H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                   24    3-CH.sub.3                                                                              S       5    H    CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                   ______________________________________                                    

                  TABLE 1c                                                        ______________________________________                                         ##STR13##                                                                    Compound No  (X).sub.n                                                                              R.sup.1   R.sup.2                                                                            R.sup.3                                  ______________________________________                                        25           5-CH.sub.3 S                                                                           H         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                          26           5-CH.sub.3                                                                             H         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                          ______________________________________                                    

The compounds of the invention may be prepared by by a variety ofmethods and in a further aspect the invention provides methods for thepreparation of compounds of formula I.

Conveniently the preparation of the compounds of the invention can beconsidered in three or four parts.

Part A involves the formation of a 5-arylcyclohexan-1,3-dione of formulaIX. This reaction may be carried out in a two step process by:

(i) reacting, preferably in the presence of a base, an aldehydederivative of formula V with acetone (IVa) or an acetone derivative offormula IVb to form a ketone derivative of formula VIa or VIbrespectively; and reacting, preferably in the presence of a base, aketone derivative of formula VIa with a malonic acid ester derivative offormula VIIa or a ketone derivative of formula VIb with a malonic acidester of formula VIIb, to give an intermediate of formula VIIIa or VIIIbrespectively which may be isolated or hydrolysed directly, preferably inthe presence of an acid, to give a 5-arylcyclohexan-1,3-dione of formulaIX, or reacting, preferably in the presence of a base, a ketonederivative of formula VIa with an alkanoic acid ester of formula VIIc togive a 5-arylcyclohexan-1,3-dione of formula IX;

(ii) reacting, preferably in the presence of a base, an aldehydederivative of formula V with a malonic acid ester of formula VIIb togive an arylmethylidenemalonate derivative of formula VIc which is inturn reacted, preferably in the presence of a base, with an acetoaceticacid derivative of formula VIId to give an intermediate of formula VIIIcwhich may be isolated or hydrolysed directly, preferably in the presenceof an acid, to give a 5-arylcyclohexan-1,3-dione of formula IX; or

(iii) reacting, preferably in the presence of a base, an aldehydederivative of formula V with an acetic acid ester of formula IVc to givea 2-arylalkenoate derivative of formula VId which is in turn reacted,preferably in the presence of a base, with an acetoacetic acid esterderivative of formula VIId to give an intermediate of formula VIIIawhich may be isolated or hydrolysed directly, preferably in the presenceof an acid, to give a 5-arylcyclohexan-1,3-dione of formula IX.

Part B involves the acylation of a compound of formula IX to give a2-acyl-5-arylcyclohexan-1,3-dione of formula XIII. This reaction may becarried out by reacting a 5-arylcyclohexan-1,3-dione of formula IX with:

(iv) an acid anhydride of formula X in the presence of either an alkalimetal salt of the corresponding acid of formula XI or an alkoxide saltof formula XII, wherein M is an alkali metal ion and R is C₁ to C₆alkyl;

(v) an acid anhydride of formula X in the presence of the correspondingacid of formula XIV;

(vi) an acid halide of formula XV, wherein hal represents halogen, inthe presence of a Lewis acid catalyst;

(vii) a mixture of an acid halide of formula XV and the correspondingacid of formula XIV; or

(viii) with an alkali or alkaline earth metal hydride followed byreaction with an acid anhydride of formula X or an acid halide offormula XV.

Alternatively, this acylation reaction may be carried out by:

(ix) reacting a 5-arylcyclohexan-1,3-dione of formula IX with an acidhalide of formula XV in the presence of pyridine to give an intermediateO-acyl derivative of formula XVI; and

(x) reacting the intermediate of formula XVI with a Lewis acid catalyst;

(xi) reacting the intermediate of formula XVI with the acid of formulaXIV; or

(xii) reacting the intermediate of formula XVI with imidazole or4-(N,N-dimethylamino)pyridine.

Part C involves the formation of a compound of the invention of formulaI wherein R¹ is hydrogen, that is a compound of formula II. Thisreaction may be carried out either by reacting a2-acyl-5-arylcyclohexan-1,3-dione of formuula XIII with:

(xiii) an alkoxyamine derivative of formula XVII; or

(xiv) hydroxylamine to give an intermediate oxime derivative of formulaXVIII and reacting that intermediate oxime derivative of formula XVIIIwith an alkylating agent of formula XIX wherein L is a leaving groupsuch as, for example, chloride, bromide, iodide, sulfate, nitrate,methyl sulfate, ethyl sulfate, tetrafluoroborate, hexafluorophosphate,hexafluoroantimonate, methanesulfonate, fluorosulfonate,methanesulfonate and trifluoromethanesulfonate.

Part D involves the formation of a compound of the invention of formulaI wherein R¹ is a substituent other than hydrogen.

Compounds of the invention of formula I, wherein R¹ forms an ether, acylor sulfonyl derivative of a compound of formula II, may be prepared fromthe corresponding compounds of the invention of formula II by reactingwith an etherification, acylation or sulfonylation reagent of formulaXX.

Compounds of the invention of formula I wherein R¹ is an inorganic ororganic cation may be prepared from the compounds of the invention offormula I wherein R¹ is hydrogen, that is, compounds of formula II, byreacting said compounds of formula II with an inorganic or organic salt.For example, the compounds of formula I wherein R¹ is an alkali metalion may be prepared by reacting the appropriate compound of formula IIwith the appropriate alkali metal hydroxide or alkoxylate. The compoundsof formula I wherein R¹ is a transition metal ion or an organic cationmay similarly be prepared by reacting the appropriate compound offormula II with an appropriate transition metal salt or organic base.Alternatively, the compounds of formula I wherein R¹ is a transitionmetal ion or an organic cation may be prepared by reacting theappropriate compound of formula I wherein R¹ is an alkali metal ion withan appropriate transition metal salt or organic salt.

Accordingly, in a further aspect the invention provides a process forthe preparation of a compound of formula I, as hereinbefore defined,which process comprises:

reacting a 2-acyl-5-(aryl)cyclohexane-1,3-dione derivative of formulaXIII with an alkoxyamine derivative of formula XVII to give a compoundof the invention of formula II or reacting the2-acyl-5-(aryl)cyclohexan-1,3-dione derivative of formula XIII withhydroxylamine and alkylating the oxime intermediate of formula XVIIIwith an alkylating agent of formula XIX, wherein L is a leaving group,to give a compound of the invention of formula II; and optionally

reacting the compound of the invention of formula II with a compound offormula XX, wherein L is a leaving group, to give a compound of theinvention of formula I.

The structures of the compounds described above are detailed on thefollowing pages wherein φ represents the group ##STR14##

Certain of the intermediate compounds of formulae V, VIa, VIb, VIc, VId,VIIIa, VIIIb, VIIIc, IX, XIII, XVI and XVIII are novel compounds andtherefore in further embodiments the invention provides novel compoundsof formulae V, VIa, VIb, VIc, VId, VIIIa, VIIIb, VIIIc, IX, XIII, XVIand XVIII and processes for the preparation thereof.

The compounds of formula I are active as herbicides and therefore, in afurther aspect the invention provides a process for severely damaging orkilling unwanted plants which process comprises applying to the plants,or to the growth medium of the plants, an effective amount of a compoundof formula I as hereinbefore defined.

Generally speaking the compounds of formula I are herbicidally effectiveagainst a variety of plants. However, certain of the compounds of theinvention are selectively active against monocotyledonous plants,dicotyledonous plants being relatively unaffected by rates ofapplication of the compounds of the invention which are severelydamaging or lethal to other plant species.

Moreover, certain of the compounds of formula I are selectively activewithin the group of monocotyledonous plants and may be used at a ratesufficient to control monocotyledonous weeds in cultivated crops,especially wild grasses in cereal crops. Certain of such compounds ofthe invention are especially useful in the control of wild grasses suchas wild oats and rye grass in crops of cultivated monocotyledonousplants such as wheat and other varieties of cereals.

Accordingly, in yet a further aspect the invention provides a processfor controlling monocotyledonous weeds in cultivated crops, especiallywild grasses in cereal crops such as wheat, which process comprisesapplying to the crop, or to the growth medium of the crop a compound offormula I, as hereinbefore defined, in an amount sufficient to severelydamage or kill the weeds but insufficient to damage the cropsubstantially.

The compounds of formula I may be applied directly to the plant(post-emergence application) or to the soil before the emergence of theplant (pre-emergence application). However, the compounds are, ingeneral, more effective when applied to the plant post-emergence.

The compounds of formula I may be used on their own to inhibit thegrowth of, severely damage, or kill plants but are preferably used inthe form of a composition comprising a compound of the invention inadmixture with a carrier comprising a solid or liquid diluent.Therefore, in yet a further aspect the invention provides plant growthinhibiting, plant damaging, or plant killing compositions comprising acompound of formula I as hereinbefore defined and an agriculturallyacceptable carrier therefor.

Certain of the compounds of formula I exhibit useful plant growthregulating activity. For example, while compounds of formula I areselectively active herbicides against wild grasses in crops ofcultivated plants at some rates of application they exhibit plant growthregulating effects in said crops.

Plant growth regulating effects may be manifested in a number of ways.For example, suppression of apical dominance, stimulation of auxiliarybud growth, stimulation of early flowering and seed formation,enhancement of flowering and increase in seed yield, stem thickening,stem shortening and tillering. Plant growth regulating effects shown bycompounds of the invention may include, for example, tillering and stemshortening in crops such as wheat and barley.

Accordingly in a still further aspect the invention provides a processfor regulating the growth of a plant which process comprises applying tothe plant, to the seed of the plant, or to the growth medium of theplant, an effective amount of a compound of formula I, as hereinbeforedefined.

To effect the plant growth regulating process of the present inventionthe compounds of formula I may be applied directly to the plant(post-emergence application) or to the seed or soil before the emergenceof the plant (pre-emergence) application.

The compounds of formula I may be used on their own to regulate thegrowth of plants but in general are preferably used in the form of acomposition comprising a compound of the invention in admixture with acarrier comprising a solid or liquid diluent. Therefore, in a stillfurther aspect the invention provides plant growth regulatingcompositions comprising a compound of formula I as hereinbefore definedand an agriculturally acceptable carrier therefor.

The compositions of the present invention may be in the form of solids,liquids or pastes. The compositions include both dilute compositionswhich are ready for immediate use and concentrated compositions whichmay require dilution before use. Therefore, the concentration of theactive ingredient in the compositions of the present invention will varydepending on the types of formulation and whether the composition isready for use such as, for example, a dust formulation or an aqueousemulsion or whether the composition is a concentrate such as, forexample, an emulsifiable concentrate or a wettable powder, which issuitable for dilution before use. In general the compositions of thepresent invention comprise from 1 ppm to 99% by weight of activeingredient.

The solid compositions may be in the form of powders, dusts, pellets,grains, and granules wherein the active ingredient is mixed with a soliddiluent. Powders and dusts may be prepared by mixing or grinding theactive ingredient with a solid carrier to give a finely dividedcomposition. Granules, grains and pellets may be prepared by bonding theactive ingredient to a solid carrier, for example, by coating orimpregnating the preformed granular solid carrier with the activeingredient or by agglomeration techniques.

Examples of solid carriers include: mineral earths and clays such as,for example, kaolin, bentonite, kieselguhr, Fuller's earth, Attaclay,diatomaceous earth, bole, loess, talc, chalk, dolomite, limestone, lime,calcium carbonate, gypsum, calcium sulfate, pyrophyllite, silicic acid,silicates and silica gels; fertilizers such as, for example, ammoniumsulfate, ammonium phosphate, ammonium nitrate and urea; natural productsof vegetable origin such as, for example, grain meals and flours, barkmeals, wood meals, nutshell meals and cellulosic powders; and syntheticpolymeric materials such as, for example, ground or powdered plasticsand resins.

Alternatively, the solid compositions may be in the form of dispersibleor wettable dusts, powders, granules or grains wherein the activeingredient and the solid carrier are combined with one or more surfaceactive agents which act as wetting, emulsifying and/or dispersing agentsto facilitate the dispersion of the active ingredient in liquid.

Examples of surface active agents include those of the cationic, anionicand non-ionic type. Cationic surface active agents include quaternaryammonium compounds, for example, the long chain alkylammonium salts suchas cetyltrimethylammonium bromide. Anionic surface active agentsinclude: soaps or the alkali metal, alkaline earth metal and ammoniumsalts of fatty acids; the alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid; the alkali metal, alkaline earthmetal and ammonium salts of arylsulfonic acids including the salts ofnaphthalenesulfonic acids such as butylnaphthalenesulfonic acids, thedi- and tri-isopropylnaphthalenesulfonic acids, the salts of thecondensation products of sulfonated naphthalene and naphthalenederivatives with formaldehyde, the salts of the condensation products ofsulfonated naphthalene and naphthalene derivatives with phenol andformaldehyde, and the salts of alkylarylbenzenesulfonic acids such asdodecylbenzenesulfonic acid; the alkali metal, alkaline earth metal andammonium salts of the long chain mono esters of sulfuric acid oralkylsulfates such as laurylsulfate and the mono esters of sulfuric acidwith fatty alcohol glycol ethers. Nonionic surface active agentsinclude: the condensation products of ethylene oxide with phenols andalkylphenols such as isooctylphenol, octylphenol and nonylphenol; thecondensation products of ethylene oxide with castor oil; the partialesters derived from long chain fatty acids and hexitol anhydrides, forexample sorbitan monolaurate, and their condensation products withethylene oxide; ethylene oxide/propylene oxide block copolymers; laurylalcohol polyglycol ether acetal; and the lecithins.

The liquid compositions may comprise a solution or dispersions of theactive ingredient in a liquid carrier optionally containing one or moresurface active agents which act as wetting, emulsifying and/ordispersing agents. Examples of liquid carriers include: water; mineraloil fractions such as, for example, kerosene, solvent naphtha,petroleum, coal tar oils and aromatic petroleum fractions; aliphatic,cycloaliphatic and aromatic hydrocarbons such as, for example, paraffin,cyclohexane, toluene, the xylenes, tetrahydronaphthalene and alkylatednaphthalenes; alcohols such as, for example, methanol, ethanol,propanol, isopropanol, butanol, cyclohexanol and propylene glycol;ketones such as, for example, cyclohexanone and isophorone; and stronglypolar organic solvents such as, for example, dimethylformamide,dimethylsulfoxide, N-methylpyrrolidone and sulfolane.

A preferred liquid composition comprises an aqueous suspension,dispersion or emulsion of the active ingredient which is suitable forapplication by spraying, atomizing or watering. Such aqueous compostionsare generally prepared by mixing concentrated compositions with water.Suitable concentrated compositions include emulsion concentrates,pastes, oil dispersions, aqueous suspensions and wettable powders. Theconcentrates are usually required to withstand storage for prolongedperiods and after such storage to be capable of dilution with water toform aqueous preparations which remain homogeneous for a sufficient timeto enable them to be applied by conventional spray equipment. Theconcentrates conveniently contain from 5 to 99%, preferably 10 to 60%,by weight of active ingredient.

Emulsion or emulsifiable concentrates are conveniently prepared bydissolving the active ingredient in an organic solvent containing one ormore surface active agents and optionally an oil. Oil dispersions may beprepared by grinding together the active ingredient, a hydrocarbon oil,and one or more surface active agents. Aqueous suspension concentratesmay conveniently be prepared by ball milling a mixture of the activeagent and preferably at least one suspending agent. Suitable suspendingagents include: hydrophilic colloids such as, for example,poly(N-vinylpyrrolidone), sodium carboxymethylcellulose and thevegetable gums, gum acacia and gum tragacanth; hydrated colloidalmineral silicates such as, for example, montmorillonite, beidellite,nontronite, hectorite, saponite, sauconite and bentonite; othercellulose derivatives; and poly(vinyl alcohol). Wettable powderconcentrates may conveniently be prepared by blending together theactive ingredients, one or more surface active agents, one or more solidcarriers and optionally one or more suspending agents and grinding themixture to give a powder having the required particle size.

The aqueous suspensions, dispersions or emulsions may be prepared fromthe concentrated compositions by mixing the concentrated compositionswith water optionally containing surface active agents and/or oils.

It should be noted that the compounds of the invention of formula Iwherein R¹ is hydrogen are acidic. Therefore, the compounds of formula Imay be formulated and applied as the salts of organic or inorganicbases. In formulating and employing the compounds of formula I in theform of their salts either the salts per se, that is the compounds offormula I wherein R¹ is an inorganic or an organic cation, may be usedin the formulation or the compounds of formula I wherein R¹ is hydrogenmay be used in the formulation and the salts generated in situ by theuse of the appropriate organic or inorganic base.

The mode of application of the compositions of the invention will dependto a large extent on the type of composition used and the facilitiesavailable for its application. Solid compositions may be applied bydusting or any other suitable means for broadcasting or spreading thesolid. Liquid compositions may be applied by spraying, atomizing,watering, introduction into the irrigation water, or any other suitablemeans for broadcasting or spreading the liquid.

The rate of application of the compounds of the invention will depend ona number of factors including, for example, the compound chosen for use,the identity of the plants whose growth is to be inhibited theformulations selected for use and whether the compound is to be appliedfor foliage or root uptake. As a general guide, however, an applicationrate of from 0.005 to 20 kilograms per hectate is suitable while from0.01 to 5.0 kilograms per hectare may be preferred.

The compositions of the invention may comprise, in addition to one ormore compounds of the invention, one or more compounds not of theinvention but which possess biological activity. For example, ashereinbefore indicated the compounds of the invention are in generalsubstantially more effective against monocotyledonous plants or grassspecies than against dicotyledonous plants or broad-leaved species. As aresult, in certain applications the herbicidal use of the compounds ofthe invention alone may not be sufficient to protect a crop. Accordinglyin yet a still further embodiment the invention provides a herbicidalcomposition comprising a mixture of at least one herbicidal compound offormula I as hereinbefore defined with at leat one other herbicide.

The other herbicide may be any herbicide not having the formula I. Itwill generally be a herbicide having a complementary action. Forexample, one preferred class is of mixtures comprising a herbicideactive against broad-leaved weeds. A second preferred class is ofmixtures comprising a contact herbicide.

Examples of useful complementary herbicides include:

A. benzo-2,1,3,-thiadiazin-4-one-2,2-dioxides such as3-isopropylbenzo-2,1,3-thiadiazin-4-one-2,2-dioxide (common namebentazon);

B. hormone herbicides and in particular the phenoxyalkanoic acids suchas 4-chloro-2-methylphenoxy acetic acid (common name MCPA),2-(2,4-dichlorophenoxy)propionic acid (common name dichlorprop),2,4,5-trichlorophenoxyacetic acid (common name 2,4,5-T),4-(4-chloro-2-methylphenoxy)butyric acid (common name MCPB),2,4-dichlorophenoxyacetic acid (common name 2,4-D),4-(2,4-dichlorophenoxy)butyric acid (common name 2,4-DB),2-(4-chloro-2-methylphenoxy)propionic acid (common name mecoprop), andtheir derivatives (eg salts, esters, amides and the like);

C. 3-[4-(4-halophenoxy)phenyl]-1,1-dialkylureas such as3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea (common namechloroxuron);

D. dinitrophenols and their derivatives (eg acetates) such as2-methyl-4,6-dinitrophenol (common name DNOC),2-tertiarybutyl-4,6-dinitrophenol (common name dinoterb),2-secondarybutyl-4,6-dinitrophenol (common name dinoseb) and its esterdinoseb acetate;

E. dinitroaniline herbicides such asN',N'-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine (commonname dinitramine), 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline(common name trifluralin) and4-methylsulfonyl-2,6-dinitro-N,N-dipropylaniline (common name nitralin);

F. phenylurea herbicides such asN'-(3,4-dichlorophenyl)-N,N-dimethylurea (common name diruon) andN,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (common namefluometuron);

G. phenylcarbamoyloxyphenylcarbamates such as3-[(methoxycarbonyl)amino]phenyl (3-methylphenyl)carbamate (common namephenmedipham) and 3-[(ethoxycarbonylamino]phenyl phenylcarbamate (commonname desmedipham);

H. 2-phenylpyridazin-3-ones such as5-amino-4-chloro-2-phenylpyridazin-3-one (common name pyrazon);

I. uracil herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil (commonname lenacil), 5-bromo-3-sec-butyl-6-methyluracil (common name bromacil)and 3-tert-butyl-5-chloro-6-methyluracil (common name terbacil);

J. triazine herbicides such as2-chloro-4-ethylamino-6-(iso-propylamino)-1,3,5-triazine (common nameatrazine). 2-chloro-4,6-di(ethylamino)-1,3,5-triazine (common namesimazine) and 2-azido-4-(iso-propylamino)-6-methylthio-1,3,5-triazine(common name aziproptryne);

K. 1-alkoxy-2-alkyl-3-phenylurea herbicides such as3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (common name linuron),3-(4-chlorophenyl)-1-methoxy-1-methylurea (common name monolinuron) and3-(4-bromo-4-chlorophenyl)-1-methoxy-1-methylurea (common namechlorobromuron);

L. thiolcarbamate herbicides such as S-propyl dipropylthiocarbamate(common name verolate);

M. 1,2,4-triazin-5-one herbicides such as4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazine-5-one (common namemetamitron) and 4-amino-6-tert-butyl4,5-dihydro-3-methylthio-1,3,4-triazin-5-one (common name metribuzin);

N. benzoic acid herbicides such as 2,3,6-trichlorobenzoic acid (commonname 2,3,6-TBA), 3,6-dichloro-2-methoxybenzoic acid (common namedicamba) and 3-amino-2,5-dichlorobenzoic acid (common name chloramben);

O. anilide herbicides such asN-butoxymethyl-α-chloro-2',6'-diethylacetanilide (common namebutachlor), the corresponding N-methoxy compound (common name alachlor),the corresponding N-isopropyl compound (common name propachlor) and3',4'-dichloropropionanilide (common name propanil);

P. dihalobenzonitrile herbicides such as 2,6-dichlorobenzonitrile(common name dichlobenil), 3,5-dibromo-4-hydroxybenzonitrile (commonname bromoxynil) and 3,5-diiodo-4-hydroxybenzonitrile (common nameioxynil);

Q. haloalkanoic herbicides such as 2,2-dichloropropionic acid (commonname dalapon), trichloroacetic acid (common name TCA) and salts thereof;

R. diphenylether herbicides such as 4-nitrophenyl2-nitro-4-trifluoromethylphenyl ether (common name fluorodifen), methyl5-(2,4-dichlorophenoxy)-2-nitrobenzoate (common name bifenox),2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid and2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitrophenyl ether;

S. N-(heteroarylaminocarbonyl)benzenesulfonamides such as2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide(commonly known as DPX 4189); and

T. miscellaneous herbicides including N,N-dimethyldiphenylacetamide(common name diphenamid), N-(1-naphthyl)phthalamic acid (common namenaptalam) and 3-amino-1,2,4-triazole.

Examples of useful contact herbicides include:

U. bipyridylium herbicides such as those in which the active entity isthe 1,1'-dimethyl-4,4'-dipyridylium ion (common name paraquat) and thosein which the active entiry is the 1,1'-ethylene-2,2'-dipyridylium ion(common name diquat);

V. organoarsenical herbicides such as monosodium methanearsonate (commonname MSMA); and

W. amino acid herbicides such as N-(phosphonomethyl)glycine (common nameglyphosate) and its salts and esters.

The invention is now illustrated by but in no way limited to thefollowing Examples.

EXAMPLE 1

This example details the preparation of the heterocyclic aldehydes offormula V which were used in the preparation of the compounds of theinvention of formula I.

Method A: The aldehydes were prepared by the condensation ofbromomalondialdehyde with the appropriate thiocarbamide following thegeneral method described in German Pat. No. 1 182 234 (Chem. Abstracts62: 7764d). The products were characterized by proton magnetic resonancespectroscopy and the details are recorded in Table 2 below.

Method B: The aldehydes were prepared from the corresponding bromosubstituted heterocycle using n-butyllithium and N-formylpiperidinefollowing the general method described by Buttimore et al (J. Chem.Soc., 2032, 1963). The products were characterized by proton magneticresonance spectroscopy and the details are recorded in Table 2 below.

Method C: The aldehydes were prepared from the corresponding parentheterocycle by lithiation with n-butyl lithium, followed by formylationwith N-formylpiperidine following the general method described by P.Iverson et al (Acta Chem. Scand., 20, 2649 (1966)). The products werecharacterized by proton magnetic resonance spectroscopy and the detailsare recorded in Table 2 below.

Method D: The aldehydes were prepared from the appropriate methylsubstituted heterocycle following the method of F Krohnke (Angew. Chem.Internat. Edit., 2, 380 (1963)). The products were characterized byproton nuclear magnetic resonance soectroscopy and the details arerecorded in Table 2 below.

                                      TABLE 2                                     __________________________________________________________________________    Aldehyde Precursors to the Compounds of Formula I                                                 Method and/or                                                                         Proton Chemical                                                       Literature                                                                            Shift δ in                                  (X).sub.n      E Link                                                                             Reference                                                                             ppm (CDCl.sub.3)                                  __________________________________________________________________________     ##STR15##                                                                    all H            2  B       Not recorded.                                     4,5-(CH.sub.3).sub.2                                                                           2  B       2.44(3H,s); 2.48(3H,s);                                                       9.83(1H,s)                                        2-CH.sub.3       5  A       2.78(3H,s); 8.22(1H,s);                                               (Chem Abs.                                                                            9.91(1H,s).                                                           62; 7764d)                                                2-C.sub.6 H.sub.5                                                                              5  A       7.35-7.50(3H,m); 7.85-                                                (Chem Abs.                                                                            8.05(2H,m); 8.34(1H,s);                                               62; 7764d)                                                                            9.96(1H,s).                                       2,4-(CH.sub.3).sub.2                                                                           5  B       2.70(3H,s); 2.74(3H,s);                                                       10.02(1H,s).                                      2-CH.sub.3       4  Chem. Ber.,                                                                           2.78(3H,s); 8.08(1H,s);                                               101, 3872                                                                             9.97(1H,s).                                                           (1968)                                                    2-CH.sub.3 S     5  A       2.67(3H,s); 8.14(1H,s);                                                       9.85(1H,s).                                       2-(CH.sub.3).sub.2 N4-CH.sub.3                                                                 5  J. Chem.                                                                              2.52(3H,s); 3.20(6H,s);                                               Soc Perkin                                                                            9.72(1H,s).                                                           Trans I, 341                                                                  1983                                                      4-CH.sub.3       2  C       2.58(3H,s); 7.39(1H,s);                                                       10.00(1H,s).                                      5-Br4-CH.sub.3   2  D       not recorded                                      5-(CH.sub.3OCH.sub.2 CH.sub.2)4-CH.sub.3                                                       2  C       2.48(3H,s); 3.07(2H,t);                                                       3.38(3H,s); 3.62(2H,t);                                                       9.86(1H,s).                                       2-Cl             5  C       8.20(1H,s); 9.96(1H,s).                           2-CH.sub.3 O     5  C       4.19(3H,s); 7.86(1H,s);                                                       9.8(1H,s).                                        5-CH.sub.3       2  C       2.57(3H,s); 7.72(1H,s);                                                       9.89(1H,s).                                        ##STR16##                                                                    3,5-(CH.sub.3).sub.2                                                                         O 4  J. Chem. Soc.,                                                                        2.46(3H,s); 2.69                                                      Perkin Trans                                                                          (3H,s); 9.92                                                          I, 570, 1976                                                                          (1H,s).                                           3-CH.sub.3     S 5  B       2.57(3H,s); 7.53                                                      (J. Chem Soc.,                                                                        (1H,s); 10.03(1H,                                                     2032, 1963)                                                                           s).                                                ##STR17##                                                                    5-CH.sub.3 S        D       2.88(3H,s); 10.09(1H,                                                         s).                                               5-CH.sub.3          D       2.8(3H,s); 10.2(1H,s).                                                (Chem. Abs.                                                                   54; 5627b)                                                __________________________________________________________________________

EXAMPLE 2

Preparation of 1-(heterocyclyl)but-1-en-3-ones

The 1-(heterocyclyl)but-1-en-3-ones used in the preparation of thecompounds of the invention of formula I were prepared from theappropriate heterocyclic aldehyde by one of the following methods:

(a) An aqueous solution of 2% sodium hydroxide (3 ml) was added to asolution of 2-methyl-thiazole-5-carboxaldehyde (2.5 g) in acetone (20ml) and water (10 ml). The mixture was stirred for 24 hours at ambienttemperature, diluted with water (150 ml) and extracted with chloroform(2×50 ml). The organic layer was washed with water then dried overanhydrous magnesium sulphate and filtered. Evaporation of the solventgave 1-(2-methyl-5-thiazolyl)but-1-en-3-one as a low-melting point solid(1.4 g, 43%). Pmr spectrum (CDCl₃ ; δ in ppm): 2.30 (3H, s); 2.72 (3H,s); 6.36 (1H, d); 7.56 (1H, d); 7.74 (1H, s).

(b) A solution of 2,4-dimethylthiazole-5-carboxaldehyde (2.0 g) and1-triphenylphosphoranylidene-2-propane (8.2 g) in dimethylsulphoxide(140 ml) was stirred at ambient temperature for 24 hr. The solution waspoured into water (400 ml) and extracted with dichloromethane. The dried(Na₂ SO₄) organic extract was evaporated and the residue was purified bycolumn chromatography over silica with ethyl acetate/n-hexane (1:1 v/v)elution to give 1-(2,4-dimethyl-5-thiazolyl)but-1-en-3-one (2.1 g) Pmrspectrum (CDCl₃ ; δ in ppm): 2.32 (3H, s); 2.49 (3H, s); 2.67 (3H, s);6.30 (1H, d); 7.60 (1H, d).

The specific method used for the preparation of each1-(heterocyclyl)but-1-en-3-one is indicated in Eample 4, Table 5.

EXAMPLE 3

Preparation of 2-acyl-3-hydroxy-5-(heterocyclyl)cyclohex-2-en-1-ones

The 2-acyl-3-hydroxy-5-(heterocyclyl)cyclohex-2-en-1-ones used in thepreparation of the compounds of the invention of formula I were preparedfrom the appropriate 1-(heterocyclyl)but-1-en-3-one either by Method (a)below, or by Method (b) below which involves isolation of theintermediate 3-hydroxy-5-(heterocyclyl)cyclohex-2-en-1-one.

(a) Diethyl malonate (1.5 g) was added to a solution of sodium (0.22 g)in dry absolute ethanol (20 ml) and the mixture was warmed to 60° C.with stirring. 1-(2-Methyl-5-thiazolyl)-but-1-en-3-one (1.4 g) was addedand the mixture was boiled under reflux for 2 hours. The ethanol wasthen completely removed under reduced pressure and dry dimethylformamide(20 ml) was added to the residue. The mixture was heated with stirringunder nitrogen to 110° C. and n-butyric anhydride (1.5 ml) was added.After 30 min, the solvent was removed under reduced pressure. An aqueoussodium hydroxide solution (1.5 g in 50 ml) was added to the residue andthe mixture was heated under reflux for 5 hours. The hot solution wasacidified (to pH 4.5) by slow addition of a dilute hydrochloric acidsolution. The cooled mixture was extracted with chloroform (2×100 ml).The dried (MgSO₄) organic layer was evaporated to give 2-butyryl-3-hydroxy-5-(2-methyl-5-thiazolyl)cyclohex-2-en-1-one (0.7 g;30%) as low melting-point solid. Pmr spectrum (CDCl₃ ; δ in ppm): 1.0(3H, t); 1.7 (2H, m); 2.68 (3H, s); 2.5-3.8 (7H, m); 7.38 (1H, s); OHnot observed.

(b) (i) Diethyl malonate (1.16 g) was added to a solution of sodium (158mg) in dry absolute ethanol (10 ml) and the mixture was heated toreflux. 1-(2-Thiazolyl)but-1-en-3-one (1.0 g) in dry absolute ethanol (5ml) was added dropwise to the solution. After refluxing for 2.5 hr, anaqueous potassium hydroxide solution (862 mg in 12 ml) was added and themixture was extracted with diethyl ether. The aqueous layer was heatedto 70° C. and neutralised with dilute hydrochloric acid and the waterwas then evaporated under reduced pressure. The residue was extractedwith dry dimethylformamide. Evaporation of the solvent gave3-hydroxy-5-(2-thiazolyl)cyclohex-2-en-1-one.

(ii) Sodium hydride (135 mg) was added to a solution of3-hydroxy-5-(2-thiazolyl)cyclohex-2-en-1-one. (1.0 g) in drydimethylformamide (20 ml). The mixture was heated to 60° C. undernitrogen. n-Butyric anhydride (886 mg) was added and the mixture wasstirred and heated at 120° C. for 2.5 hr. After cooling, the mixture waspoured into a dilute hydrochloric acid solution which was then extractedwith dichloromethane. The organic extract was evaporated and the residuewas heated at reflux with an aqueous potassium hydroxide solution (2 gin 50 ml) for 0.5 hr. After cooling, the solution was washed withdichloromethane (15 ml). The aqueous layer was acidified with dilutehydrochloric acid and the mixture was then extracted with ethyl acetate.The dried (MgSO₄) organic extract was evaporated and the residue waspurified by column chromatography over silica to give2-butyryl-3-hydroxy-5-(2-thiazolyl)cyclohex-2-en-1-one as anorange-brown oil. Pmr spectrum (CDCl₃ ; δ in ppm): 0.96 (3H, t);1.44-1.84 (2H, m); 3.00-3.12 (6H, m); 3.68-4.00 (1H, m); 7.28 (1H, d);7.72 (1H, d); 18.20 (1H, brs).

All products were characterized by proton nuclear magnetic resonancespectroscopy. Physical data for the3-hydroxy-5-(heterocyclyl)cyclohex-2-en-1-ones prepared according tomethod (b) (i) above are recorded in Table 3 below. Physical data andspectroscopic data for the2-acyl-3-hydroxy-5-(heterocyclyl)cyclohex-2-en-1-ones prepared accordingto Method (a) and Method (b) (ii) above are recorded in Table 4 below.The specific Method used for the preparation of each2-acyl-3-hydroxy-5-(heterocyclyl)cyclohex-2-en-1-one is indicated inExample 4, Table 5.

                  TABLE 3                                                         ______________________________________                                         ##STR18##                     IX                                             Intermediate of                                                               Formula IX Used                                                               in the                    Proton Chemical                                     Preparation of            Shift (δ in                                   Compound No(s)                                                                              Appearance  ppm, DMSOd.sub.6)                                   ______________________________________                                         1            White solid 2.4-4.0(5H,m); 5.48                                                           (1H,s); 7.2-7.6                                                               (2H,dofd); 10.5(1H,                                                           brs).                                               10            Brown       2.32(3H,s); 2.3-4.0                                               solid       (5H,m); 5.50(1H,s);                                                           9.0(1H,brs).                                        ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                         ##STR19##                    XIII                                            Intermediate of                                                               Formula XIII Used                                                             in the                   Proton Chemical                                      Preparation of           Shift (δ  in                                   Compound No(s)                                                                            Appearance   ppm, CDCl.sub.3)                                     ______________________________________                                        1           Orange-brown 0.96(3H,t); 1.44-                                                oil          1.84(2H,m); 3.00-3.12                                                         (6H,m); 3.68-4.00(1H,                                                         m); 7.28(1H,d); 7.72                                                          (1H,d); 18.20(1H,brs).                               2, 20       Pale brown   0.98(3H,t); 1.4-1.8                                              solid        (2H,m); 2.29(3H,s);                                                           2.31(3H,s); 2.7-3.9                                                           (7H,m); 18.2(1H,s),                                  3           Brown oil    1.0(3H,t); 1.45-1.85                                                          (2H,m); 2.68(3H,s);                                                           2.5-3.8(H,m); 7.38                                                            (1H,s). OH not                                                                observed.                                            5           Brown oil    0.99(3H,t); 1.64(2H,                                                          m); 2.32(3H,s); 2.62                                                          (3H,s); 2.30-3.85(7H,                                                         m); 18.25(1H,s).                                     6, 17, 18, 19,                                                                            Pale-brown   0.98(3H,t); 1.45-1.85                                21          solid        (2H,m); 2.69(3H,s);                                                           2.7-3.8(7H,m); 6.80                                                           (1H,s); 18.26(1H,s).                                 7           Brown solid  1.13(3H,t); 2.65(3H,                                                          s); 2.7-3.7(7H,m);                                                            7.30(1H,s); 18.18                                                             (1H,s).                                              8           Pale yellow  1.00(3H,t); 1.5-1.8                                              solid, mp    (2H,m); 2.18(3H,s);                                              130°  2.5-3.0(6H,m); 3.07                                                           (6H,s); 3.27-3.67(1H,                                                         m); 18.31(1H,s).                                     9           Pale yellow  0.97(3H,t); 1.45-1.75                                            oil          (2H,m); 2.2-3.9(7H,                                                           m); 2.43(3H,s); 6.80                                                          (1H,s); 18.26(1H,s).                                 10          Brown oil    1.13(3H,t); 2.35                                                              (3H,s); 2.3-3.8(7H,                                                           m); 18.21(1H,s).                                     11          Orange oil   Not recorded                                         12          White solid  1.15(3H,t); 2.5-                                                 mp 80° C.                                                                           3.79(7H,m); 7.34                                                              (1H,s); 18.25(1H,s).                                 13          Yellow solid,                                                                              1.15(3H,t); 2.6-                                                 mp 91° C.                                                                           3.21(6H,m); 3.33-                                                             3.67(1H,m); 4.05(3H,                                                          s); 6.89(1H,s);                                                               18.31(1H,s).                                         14          Pale yellow  1.14(3H,t); 2.46(3H,                                             solid, mp 73° C.                                                                    s); 2.75-3.20(6H,m);                                                          3.42-3.84(1H,m);                                                              7.36(1H,s); 18.21                                                             (1H,s).                                              15          Pale brown   1.14(3H,t); 2.30                                                 solid        (3H,s); 2.32(3H,s);                                                           2.7-3.7(7H,m);                                                                18.22(1H,s).                                         22          Orange oil   1.16(3H,t); 2.26                                                              (3H,s); 2.37(3H,s);                                                           2.5-3.6(7H,m);                                                                18.17(1H,s).                                         23, 24      Pale yellow  1.10(3H,t); 2.47                                                 oil          (3H,s); 2.34-3.34                                                             (6H,m); 3.47-4.14                                                             (1H,m); 6.81(1H,s);                                                           18.2(1H,brs).                                        25          Orange oil   1.14(3H,t); 2.77(3H,                                                          s); 2.7-4.0(7H,m);                                                            18.23(1H,s).                                         26          Brown oil    1.14(3H,t); 2.75                                                              (3H,s); 2.7-4.0(7H,                                                           m); 18.2(1H,brs).                                    ______________________________________                                    

EXAMPLE 4

Preparation of the compounds of the invention of formula I

The compounds of the invention of formula I indicated in Table 1 wereprepared from the appropriate2-acyl-3-hydroxy-5-(heterocyclyl)cyclohex-2-en-1-one by one of methods(a) to (d) below.

(a)2-[1-(Ethoxyimino)butyl]-3-hydroxy-5-(2-methyl-5-thiazolyl)cyclohex-2-en-1-one(3)

Ethoxyamine hydrochloride (0.3 g) and then aqueous sodium hydroxide(0.12 g in 1 ml of water) were added to a solution of2-butyryl-3-hydroxy-5-(2-methyl-5-thiazolyl)cyclohex-2-en-1-one (0.7 g)in ethanol (50 ml) at 20° C. with stirring. After 20 hours, the mixturewas diluted with water (200 ml) and then extracted with chloroform(2×100 ml). The dried (MgSO₄) organic extract was evaporated to give2-[1-ethoxyimino)butyl]-3-hydroxy-5-(2-methyl-5-thiazolyl)cyclohex-2-en-1-one(0.75 g, 95%) as a nearly colourless oil which was characterised byproton magnetic resonance spectroscopy (CDCl₃ ; δ in ppm); 0.96 (3H, t);1.31 (3H, t); 1.7 (2H, m); 2.65 (3H, s); 2.5-3.8 (7H, m); 4.10 (2H, q);7.37 (1H, s); 15.1 (1H, brs).

(b)2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-(3-methyl-5-isothiazolyl)cyclohex-2-en-1-one(23)

Ethoxyamine hydrochloride (0.638 g, 6.38 mmol) and then sodium acetate(0.523 g, 6.38 mmol) were added to a solution of2-propionyl-3-hydroxy-5-[5-(3-methylisothiazolyl]cyclohex-2-en-1-one(1.69 g, 6.38 mmol) in ethanol (40 ml). The mixture was was stirred atroom temperature overnight and then the ethanol was removed byevaporation under reduced pressure. The residue was partitioned betweenwater and dichloromethane. The organic layer was separated, dried (Na₂SO₄) and evaporated to yield2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(3-methyl-5-isothiazolyl)cyclohex-2-en-1-one(950 mg, 48%) as a light brown oil.

(c)2-[1-(Ethoxyimino)butyl]-3-benzoyloxy-5-(4,5-dimethyl-2-thiazolyl)cyclohex-2-en-1-one(20)

Benzoyl chloride (0.12 g) and 4-methylpyridine (0.08 g) were addeddropwise with stirring to a solution of2-[1-(ethoxyimino)butyl]-5-(4,5-dimethyl-2-thiazolyl)-3-hydroxycyclohex-2-en-1-one(2) (0.27 g) in dichloromethane (40 ml) at ambient temperature. After 1hour the solution was washed with cold dilute aqueous sodium hydroxide,followed by cold dilute hydrochloric acid and then dried over magnesiumsulphate and evaporated to give2-[1-(ethoxyimino)butyl]-3-benzoyloxy-5-(4,5-dimethyl-2-thiazolyl)cyclohex-2-en-1-one(0.28 g, 80%) as an orange oil. The product was characterized by protonnuclear magnetic resonance spectroscopy and appropriate physical dataare recorded in Example 5 Table 6.

(d) Sodium salt of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(2-methyl-4-thiazolyl)cyclohex-2-en-1-one(21)

2-[1-(Ethoxyimino)butyl]-3-hydroxy-5-(2-methyl-4-thiazolyl)cyclohex-2-en-1-one(6) (0.36 g) and sodium hydroxide (0.05 g) were stirred in acetone (20ml) at room temperature for 1 hour. The solvent was evaporated and theresidue was suspended in toluene (20 ml). Evaporation of the toluenegave the sodium salt of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(2-methyl-4-thiazolyl)cyclohex-2-en-1-oneas a yellow solid (0.30 g).

The specific Method employed for the preparation of each of the1-(heterocyclyl)but-1-en-3-ones of formula VIa (Example 2) and the3-hydroxy-5-(heterocyclyl)cyclohex-2-en-1-ones of formula IX (Example 3)and/or 2-acyl-3-hydroxy-5-(heterocyclyl)cyclohex-2-en-1-ones of formulaXIII (Example 3) used as intermediates in the preparation of thecompounds of the invention of formula I are listed in Table 5 below,together with the specific Method employed for the preparation of thecompounds of the invention of formula I.

Each of the compounds of the invention of formula I were characterizedby proton nuclear resonance spectroscopy and physical data andspectroscopic data are recorded in Example 5, Table 6.

                  TABLE 5                                                         ______________________________________                                                Method of Preparation of Compounds                                            of Formulae                                                                     VIa         IX and XIII                                                                              I                                            Compound  Example 2   Example 3  Example 4                                    No        Method      Method     Method                                       ______________________________________                                         1        a           b          a                                             2        a           a          a                                             3        a           a          a                                             4        a           a          a                                             5        b           a          a                                             6        b           a          a                                             7        b           a          a                                             8        a           a          b                                             9        b           a          b                                            10        b           b          b                                            11        b           a          b                                            12        b           a          b                                            13        b           a          b                                            14        b           a          b                                            15        b           a          a                                            16        b           a          b                                            17        b           a          b                                            18        b           a          b                                            19        b           a          b                                            20        a           a          c                                            21        b           a          d                                            22        b           a          b                                            23        b           a          b                                            24        b           a          b                                            25        b           a          b                                            26        b           a          b                                            ______________________________________                                    

EXAMPLE 5

The compounds of the invention of formula I were characterized by andmay be identified by their proton nuclear resonance spectra. Forconvenience physical data and pmr spectroscopic data for the compoundsof formula I are recorded in Table 6 below.

                  TABLE 6                                                         ______________________________________                                        Com-                                                                          pound                Proton Chemical Shift                                    No      Appearance   δ in ppm (CDCl.sub.3)                              ______________________________________                                         1      Orange-brown 0.96(3H,t); 1.32(3H,t); 1.55                                     oil          (2H,m); 2.86-3.9(7H,m); 4.11                                                  (2H,q); 7.27(1H,d); 7.73(1H,                                                  d); 14.00(1H,brs).                                        2      Light brown  0.95(3H,t); 1.31(3H,t); 1.53                                     solid, mp    (2H,m); 2.29(6H,s); 2.3-3.9                                      85° C.                                                                              (7H,m); 4.10(2H,q); 14.98(1H,                                                 s).                                                       3      Colourless   0.96(3H,t); 1.31(3H,t); 1.7                                      oil          (2H,m); 2.65(3H,s); 2.5-3.8                                                   (7H,m); 4.10(2H,q); 7.37(1H,                                                  s); 15.1(1H,brs).                                         4      Pale yellow  0.98(3H,t); 1.32(3H,t); 1.58                                     oil          (2H,m); 2.7-3.8(7H,m); 4.12                                                   (2H,q); 7.4-7.9(6H,m); 15.22                                                  (1H,s).                                                   5      Light brown  0.99(3H,t); 1.33(3H,t); 1.59                                     oil          (2H,m); 2.32(3H,s); 2.62(3H,                                                  s); 2.3-3.9(7H,m); 4.13(2H,                                                   q); OH not observed.                                      6      Light brown  0.96(3H,t); 1.31(3H,t); 1.5                                      solid, mp    (2H,m); 2.69(2H,s); 2.7-4.0                                      68-70° C.                                                                           (7H,m); 4.10(2H,q); 6.79(1H,                                                  s); 15.0(1H,brs).                                         7      Pale brown   1.15(3H,t); 1.33(3H,t); 2.66                                     solid        (3H,s); 2.6-3.1(6H,m); 3.4-                                                   3.8(1H,m); 4.12(2H,q); 7.39                                                   (1H,s); OH not observed.                                  8      Orange oil   0.99(3H,t); 1.32(3H,t);                                                       1.37-1.71(2H,m); 2.21(3H,s);                                                  2.46-3.00(6H,m); 3.09(6H,s);                                                  3.11-3.60(1H,m); 4.11(2H,q);                                                  15.42(1H,s).                                              9      Pale yellow  0.96(3H,t); 1.32(3H,t); 1.60                                                  (2H,m); 2.2-3.9(7H,m); 2.42                                                   (3H,s); 4.11(2H,q); 6.78(1H,                                                  s); OH not observed.                                     10      Brown oil    1.14(3H,t); 1.32(3H,t); 2.36                                                  (3H,s); 2.4-3.1(6H,m); 3.4-                                                   3.8(1H,m); 4.13(2H,q); OH not                                                 observed.                                                11      Pale yellow  0.96(3H,t); 1.32(3H,t); 1.55                                                  (2H,m); 2.2-3.9(9H,m); 2.33                                                   (3H,s); 3.37(3H,s); 3.55(2H,                                                  t); 4.11(2H,q); OH not                                                        observed.                                                12      Pale yellow  1.07-1.41(6H,m); 2.53-3.10                                       solid, mp    (6H,m); 3.44-3.73(1H,m); 4.13                                    86° C.                                                                              (2H,q); 7.34(1H,s); 15.31(1H,                                                 brs).                                                    13      Yellow solid,                                                                              1.06-1.41(6H,m); 2.55-3.10                                       mp 78° C.                                                                           (6H,m); 3.33-3.67(1H,m); 4.05                                                 (3H,s); 4.13(2H,q); 6.87(1H,                                                  s); 15.08(1H,brs).                                       14      Cream solid  1.06-1.40(6H,m); 2.45(3H,s);                                     mp 89° C.                                                                           2.75-3.15(6H,m); 3.43-3.84                                                    (1H,m); 4.12(2H,q); 7.35(1H,                                                  s); 15.10(1H,s).                                         15      Pale brown   1.14(3H,t); 1.32(3H,t); 2.30                                     solid        (6H,s); 2.6-3.1(6H,m); 3.4-                                                   3.8(1H,s); 4.13(2H,q); 15.0                                                   (1H,brs).                                                16      Yellow oil   1.06-1.44(6H,m); 2.6-4.2(11H,                                                 m); 7.3(1H,s); 15.5(1H,brs).                             17      Yellow oil   0.97(3H,t); 1.42-1.79(2H,m);                                                  2.51-3.05(6H,m); 2.68(3H,s);                                                  3.36-3.70(1H,m); 4.56(2H,d);                                                  5.24-5.49(2H,m); 5.75-6.21                                                    (1H,m); 6.78(1H,s); 14.08                                                     (1H,s).                                                  18      Yellow oil   0.94(3H,t); 1.43-1.75(2H,m);                                                  2.64-3.10(6H,m); 2.69(3H,s);                                                  3.33-3.62(1H,m); 4.07-4.19(1H,                                                m); 4.30-4.50(2H,m); 4.82-4.99                                                (1H,m); 6.79(1H,s); 14.08(1H,                                                 s).                                                      19      Yellow oil   0.94(3H,t); 1.43-1.71(2H,m);                                                  2.57-3.03(7H,m); 2.69(3H,s);                                                  3.37-3.66(1H,m); 4.63(2H,d);                                                  6.79(1H,s); 13.87(1H,s).                                 20      Orange oil   0.75-1.58(8H,m); 2.33(6H,s);                                                  2.36-3.34(6H,m); 3.72-4.09(3H,                                                m); 7.35-7.66(3H,m); 7.95-                                                    8.15(2H,m).                                              21      Pale yellow  (DMSOd.sub.6) 0.74(3H,t); 1.03-1.49                              solid        (5H,m); 2.06-2.69(6H,m); 2.60                                                 (3H,s); 3.03-3.49(1H,m); 3.89                                                 (2H,q); 7.04(1H,s).                                      22      Yellow oil   1.17(3H,t); 1.34(3H,t); 2.28                                                  (3H,s); 2.38(3H,s); 2.5-3.5(7H,                                               m); 4.14(2H,q); 15.0(1H,brs).                            23      Light brown  1.15(3H,t); 1.33(3H,t); 2.46                                     oil          (3H,s); 2.54-3.60(6H,m); 3.66                                                 (1H,m); 4.12(2H,q); 6.8(1H,s);                                                15.2(1H,brs).                                            24      Brown oil    1.15(3H,t); 2.44(3H,s); 2.61-                                                 3.04(6H,m); 3.56-3.85(1H,m);                                                  4.56(2H,d); 5.17-5.51(2H,m);                                                  5.77-6.20(1H,m); 6.83(1H,s);                                                  15.44(1H,s).                                             25      Pale brown   1.16(3H,t); 1.33(3H,t); 2.78                                     solid        (3H,s); 2.8-3.2(6H,m); 3.7-4.0                                                (1H,m); 4.13(2H,q); OH not                                                    observed.                                                26      Brown oil    1.15(3H,t); 1.33(3H,t); 2.76                                                  (3H,s); 2.8-3.1(6H,m); 3.7-4.0                                                (1H,m); 4.12(2H,q); 15.0(1H,                                                  brs).                                                    ______________________________________                                    

EXAMPLE 6

This non-limiting Example illustrates the preparation of formulations ofthe compounds of the invention.

(a) Emulsifiable Concentrate

Compound No 7 was dissolved in toluene containing 7% V/V "Teric" N13 and3% v/v "Kemmat" SC15B to give an emulsifiable concentrate which may bediluted with water to the required concentration to give an aqueousemulsion which may be applied by spraying.

("Teric" is a Trade Mark and "Teric" N13, is a product of ethoxylationof nonylphenol; "Kemmat" is a Trade Mark and "Kemmat" SC15B is aformulation of calcium dodecylbenzenesulfonate.)

(b) Aqueous Suspension

Compound No 7 (5 parts by weight) and "Dyapol" PT (1 part by weight)were added to an aqueous solution (94 parts by weight) of "Teric" N8 andthe mixture was ball milled to produce a stable aqueous suspension whichmay be diluted with water to the required concentration to give anaqueous suspension which may be applied by spraying. ("Dyapol" is aTrade Mark and "Dyapol" PT is an anionic suspending agent; "Teric" N8 isa product of ethoxylation of nonylphenol).

(c) Emulsifiable Concentrate

Compound No 7 (10 parts by weight), "Teric" N13 (5 parts by weight) and"Kemmat" SC15B (5 parts by weight) were dissolved in "Solvesso" 150 (80parts by weight) to give an emulsifiable concentrate which may bediluted with water to the required concentration to give an aqueousemulsion which may be applied by spraying. ("Solvesso" is a Trade Markand "Solvesso" 150 is a high boiling point aromatic petroleum fraction.)

(d) Dispersible Powder

Compound No 7 (10 parts by weight), "Matexil" DA/AC (3 parts by weight),"Aerosol" OT/B (1 part by weight) and china clay 298 (86 parts byweight) were blended and then milled to give a powder composition havinga particle size below 50 microns. ("Matexil" is a Trade Mark and"Matexil" DA/AC is the disodium salt of a naphthalenesulfonicacid/formaldehyde condensate; "Aerosol" i s a Trade Mark and "Aerosol"OT/B is a formulation of the dioctyl ester of sodium sulfosuccinicacid.)

(e) High Stength Concentrate

Compound No 7 (99 parts by weight), silica aerogel (0.5 parts by weight)and synthetic amorphous silica (0.5 parts by weight) were blended andground in a hammer-mill to produce a powder having a particle size lessthan 200 microns.

(f) Dusting Powder

Compound No 7 (10 parts by weight), attapulgite (10 parts by weight) andpyrophyllite (80 parts by weight) were thoroughly blended and thenground in a hammer-mill to produce a powder of particle size less than200 microns.

Emulsifiable concentrates and/or suspensions of the compounds of theinvention were prepared essentially as described in part (a), (b) or (c)above and then diluted with water, optionally containing surface activeagent and/or oil, to give aqueous compositions of the requiredconcentration which were used, as described in Examples 7 and 8, in theevaluation of the pre-emergence and post-emergence herbicidal activityof the compounds.

EXAMPLE 7

The pre-emergent herbicidal activity of the compounds of the inventionformulated as described in Example 6 was assessed by the followingprocedure:

The seeds of the test species were sown in rows 2 cm deep in soilcontained in seed boxes. The monocotyledonous plants and thedicotyledonous plants were sown in separate boxes and after sowing thetwo boxes were sprayed with the required quantity of a composition ofthe invention. Two duplicate seed boxes were prepared in the same mannerbut were not sprayed with a composition of the invention and were usedfor comparison purposes. All the boxes were placed in a glasshouse,lightly watered with an overhead spray to initiate germination and thensub-irrigated as required for optimum plant growth. After three weeksthe boxes were removed from the glass house and the effect of thetreatment was visually assessed. The results are presented in Table 7where the damage to plants is rated on a scale of from 0 to 5 where 0represents fromm 0 to 10% damage, 1 represents from 11 to 30% damage, 2represents from 31 to 60% damage, 3 represents from 61 to 80% damage, 4represents from 81 to 99% damage and 5 represents 100% kill. A dash (-)means that no experiment was carried out.

The names of the test plants are as follows:

    ______________________________________                                               Wh         Wheat                                                              Ot         Wild Oats                                                          Rg         Ryegrass                                                           Jm         Japanese millet                                                    P          Peas                                                               Ip         Ipomea                                                             Ms         Mustard                                                            Sf         Sunflower                                                   ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        Pre-emergence Herbicidal Activity                                             Com-                                                                          pound APPLICATION  TEST PLANT                                                 No    Rate (kg/ha) Wh     Ot  Rg  Jm   P   Ip  Ms  Sf                         ______________________________________                                         3    0.5          0      0   2   1    0   0   0   0                           5    1.0          0      3   4   5    0   0   0   0                           5    0.25         0      0   3   3    0   0   0   0                           6    1.0          5      4   5   5    0   0   0   0                           6    0.25         0      2   5   5    0   0   0   0                           7    1.0          3      4   5   5    0   0   0   0                           7    0.25         1      1   5   4    0   0   0   0                          12    1.0          2      5   5   5    0   0   0   0                          12    0.25         1      1   4   5    0   0   0   0                          13    1.0          3      3   4   5    0   0   0   0                          13    0.25         0      2   3   4    0   0   0   0                          17    1.0          2      2   5   5    0   0   0   0                          17    0.25         --     1   2   3    0   0   0   0                          18    1.0          2      2   1   5    0   0   0   0                          18    0.25         --     2   --  --   0   0   0   0                          19    1.0          2      2   5   5    0   0   0   0                          22    1.0          5      5   5   5    0   0   0   0                          22    0.25         5      5   5   3    0   0   0   0                          23    1.0          3      4   5   5    0   0   0   0                          26    1.0          5      5   5   5    0   0   0   0                          ______________________________________                                    

EXAMPLE 8

The post-emergent herbicidal activity of the compounds of the inventionformulated as described in Example 6 was assessed by the followingprocedure.

The seeds of the test species were sown in rows 2 cm deep in soilcontained in seed boxes. The monocotyledonous plants and thedicotyledonous plants were sown in separate seed boxes in duplicate. Thefour seed boxes were placed in a glass house, lightly watered with anoverhead spray to initiate germination and then sub-irrigated asrequired for optimum plant growth. After the plants had grown to aheight of about 10 to 12.5 cm one box of each of the monocotyledonousplants and the dicotyledonous plants was removed from the glass houseand sprayed with the required quantity of a composition of theinvention. After spraying the boxes were returned to the glass house fora further 3 weeks and the effect of treatment was visually assessed bycomparison with the untreated controls. The results are presented inTable 8 where the damage to plants is rated on a scale of from 0 to 5where 0 represents from 0 to 10% damage, 1 represents from 11 to 30%damage, 2 represents from 31 to 60% damage, 3 represents from 61 to 80%damage, 4 represents from 81 to 99% damage and 5 represents 100% kill. Adash (-) means that no experiment was carried out.

The names of the test plants are as follows:

    ______________________________________                                               Wh         Wheat                                                              Ot         Wild Oats                                                          Rg         Ryegrass                                                           Jm         Japanese millet                                                    P          Peas                                                               Ip         Ipomea                                                             Ms         Mustard                                                            Sf         Sunflower                                                   ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        Post-emergence Herbicidal Activity                                            Com-                                                                          pound APPLICATION  TEST PLANT                                                 No    Rate (kg/ha) Wh     Ot  Rg  Jm   P   Ip  Ms  Sf                         ______________________________________                                         1    1.0          3      4   4   4    0   0   0   0                           1    0.25         0      1   4   3    0   0   0   0                           2    1.0          0      4   4   5    0   0   0   0                           2    0.25         0      4   2   3    0   0   0   0                           3    0.5          5      5   5   5    0   0   0   0                           3    0.25         --     5   5   5    0   0   0   0                           3    0.063        3      5   5   5    0   0   0   0                           4    1.0          0      4   4   3    0   0   0   0                           5    1.0          5      5   5   5    0   0   0   0                           5    0.25         4      5   5   5    0   0   0   0                           5    0.063        1      4   4   5    0   0   0   0                           6    1.0          5      5   5   5    0   0   0   0                           6    0.25         1      5   5   5    0   0   0   0                           6    0.063        0      3   5   5    0   0   0   0                           7    1.0          5      5   5   5    0   0   0   0                           7    0.25         5      5   5   5    0   0   0   0                           7    0.063        5      5   5   5    0   0   0   0                          17    1.0          4      5   5   5    0   0   0   0                          17    0.25         2      5   5   5    --  --  --  --                         17    0.063        --     1   4   5    --  --  --  --                         18    1.0          4      5   5   5    0   0   0   0                          18    0.25         4      5   5   5    --  --  --  --                         18    0.063        --     5   5   5    --  --  --  --                         19    1.0          5      5   5   5    0   0   0   0                          19    0.25         1      3   4   5    --  --  --  --                         19    0.063        --     1   3   5    --  --  --  --                         22    1.0          5      5   5   5    0   0   0   0                          22    0.25         5      5   5   5    0   0   0   0                          22    0.063        5      5   3   5    0   0   0   0                          23    1.0          5      5   5   5    0   0   0   0                          23    0.25         5      5   5   5    0   0   0   0                          23    0.063        0      4   4   5    0   0   0   0                          25    1.0          4      4   4   3    0   0   0   0                          25    0.25         3      4   3   4    0   0   0   0                          26    1.0          5      5   5   5    0   0   0   0                          26    0.25         5      5   5   5    0   0   0   0                          26    0.063        3      3   5   5    0   0   0   0                          ______________________________________                                    

EXAMPLE 9

The compounds were formulated for test by mixing an appropriate amountwith 5 ml of an emulsion prepared by diluting 160 ml of a solutioncontaining 21.9 g per liter of "Span" 80 and 78.2 g liter of "Tween" 20in methylcyclohexanone to 500 ml with water. "Span" 80 is a Trade Markfor a surface-active agent comprising sorbitan monolaurate. "Tween" 20is a Trade Mark for a surface-active agent comprising a condensate ofsorbitan monolaurate with 20 molor proportions of ethylene oxide. Each 5ml emulsion containing a test compound was then diluted to 40 ml withwater and sprayed on to young pot plants (post-emergence test) of thespecies named in Table 9 below. Damage to test plants was assessed after14 days on a scale of 0 to 5 wherein 0 is 0 to 20% damage and 5 iscomplete kill. In a test for pre-emergance herbicidal activity, seeds ofthe test plants were sown in a shallow slit formed in the surface ofsoil in fibre trays. The surface was then levelled and sprayed, andfresh soil then spread thinly over the sprayed surface. Assessment ofherbicidal damage was carried out after 21 days using the same scale of0 to 5 as the post-emergence test. In both cases the degree ofherbicidal damage was assessed by comparison with untreated controlplants. the results are given in Table 9 below. A dash (-) means noexperiment was carried out.

The names of the test plants were as follows:

    ______________________________________                                        Mz              Maize                                                         Ww              Winter wheat                                                  Rc              Rice                                                          Br              Barley                                                        Av              Avena fatua                                                   Dg              Digitaria sanguinalis                                         Al              Alopecurus myosuroides                                        St              Setaria viridis                                               Ec              Echinochloa crus-galli                                        Sh              Sorghum halepense                                             Ag              Agropyron repens                                              ______________________________________                                    

                                      TABLE 9                                     __________________________________________________________________________          APPLICATION                                                             Compound                                                                            Method Rate                                                                            TEST PLANT                                                     No    (kg/ha)  Mz Ww Rc                                                                              Br                                                                              Av Dg Al                                                                              St                                                                              Ec                                                                              Sh                                                                              Ag                                     __________________________________________________________________________    1     PRE  0.2 2  2  4 --                                                                              4  3  4 2 4 --                                                                              3                                      1     POST 0.2 4  2  3 --                                                                              4  4  4 4 4 4 2                                      2     POST 0.4 4  1  4 --                                                                              4  2  3 3 4 3 0                                      3     POST 0.4 4  4  4 --                                                                              4  4  4 5 5 4 4                                      3     POST 0.2 4  3  4 --                                                                              4  4  4 4 5 4 4                                      3     POST 0.05                                                                              4  0  3 --                                                                              2  3  4 3 4 3 0                                      4     POST 0.4 3  0  3 --                                                                              3  2  4 3 4 3 0                                      4     POST 0.2 2  0  1 --                                                                              3  1  4 3 4 1 0                                      5     POST 0.4 4  4  4 --                                                                              4  4  4 4 5 4 4                                      5     POST 0.2 4  3  4 --                                                                              4  4  4 4 4 4 3                                      5     POST 0.05                                                                              4  0  1 --                                                                              0  3  3 3 3 3 0                                      6     POST 0.4 3  3  4 --                                                                              5  4  4 5 5 4 3                                      6     POST 0.2 3  2  4 --                                                                              4  3  4 4 4 2 2                                      6     POST 0.05                                                                              2  0  4 --                                                                              4  2  3 4 2 1 1                                      7     POST 0.4 4  3  4 --                                                                              5  4  --                                                                              4 5 4 3                                      7     POST 0.2 4  3  4 --                                                                              5  4  --                                                                              3 4 4 1                                      7     POST 0.05                                                                              2  1  4 --                                                                              4  3  --                                                                              3 4 4 1                                      8     POST 0.4 4  2  4 --                                                                              3  4  4 4 4 4 0                                      8     POST 0.2 4  1  4 --                                                                              1  4  3 3 4 4 0                                      9     POST 0.4 4  1  4 --                                                                              4  4  4 4 4 4 2                                      9     POST 0.2 4  0  4 --                                                                              4  4  4 5 4 --                                                                              1                                      9     POST 0.05                                                                              1  0  1 --                                                                              0  3  3 3 3 3 0                                      10    POST 0.2 2  0  2 --                                                                              3  4  4 2 4 4 0                                      15    POST 0.2 4  0  4 --                                                                              4  4  --                                                                              3 4 4 0                                      15    POST 0.1 2  0  2 --                                                                              4  3  --                                                                              2 4 2 0                                      22    POST 0.2 4  4  4 --                                                                              4  2  4 4 4 4 4                                      22    POST 0.1 4  4  4 --                                                                              4  3  4 4 4 4 3                                      25    POST 0.4 4  4  4 --                                                                              4  4  4 4 4 4 4                                      25    POST 0.2 3  2  2 --                                                                              4  3  4 4 4 4 3                                      25    POST 0.1 2  0  0 --                                                                              3  3  3 3 2 4 1                                      26    POST 0.2 5  4  4 --                                                                              4  4  4 4 4 4 2                                      26    POST 0.05                                                                              4  0  1 --                                                                              2  4  3 4 4 3 0                                      __________________________________________________________________________

We claim:
 1. A compound of formula ##STR20## wherein: E is selected fromoxygen and sulfur;X is selected from the group consisting of C₁ to C₃alkyl, C₁ to C₃ alkoxy and C₁ to C₃ alkylthio; R¹ is selected from thegroup consisting of hydrogen and the alkali metals; R² is selected fromthe group consisting of C₁ to C₃ alkyl, allyl and propargyl; R³ isselected from the group consisting of C₁ to C₃ alkyl; and R⁴ ishydrogen.
 2. A compound according to claim 1 wherein:E is selected fromoxygen and sulfur; X is selected from the group consisting of methyl,methoxy, and methylthio; R¹ is selected from the group consisting ofhydrogen, sodium and potassium; R² is selected from the group consistingof ethyl, allyl and propargyl; R³ is selected from ethyl and n-propyland; R⁴ is hydrogen.
 3. A compound according to claim 2 of formula##STR21## wherein X, is selected from methyl and methylthio;R¹ and R⁴are both hydrogen; and R² and R³ are both ethyl.
 4. A compound accordingto claim 2 which is2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(5-methylthio-1,3,4-thiadiazol-2-yl)cyclohex-2-en-1-one.5. A herbicidal composition comprising as active ingredient a compoundas defined according to claim 1 and a carrier therefor.
 6. A process forseverely damaging or killing unwanted plants which process comprisesapplying to said plants, or to the growth medium of said plants, aneffective amount of a compound as defined according to claim
 1. 7. Aprocess for selectively controlling the growth of monocotyledonous weedsin dicotyledonous crops which process comprises applying to said crop,or to the growth medium of said crop, a compound as defined according toclaim 1 in an amount sufficient to severely damage or kill said weedsbut insufficient to substantially damage said crop.
 8. A processaccording to claim 6 or claim 7 wherein the compound is applied at arate in the range of from 0.005 to 20 kilograms per hectare.